USOO9505701 B2 (12) United States Patent (10) Patent No.: US 9,505,701 B2 Garbark et al. (45) Date of Patent: Nov. 29, 2016 (54) METHOD FOR THE PRODUCTION OF 2,566,559 A * 9, 1951 Dolnick .................. CO7C 41.56 ESTERS AND USES THEREOF 568/605 2,813,113 A 11/1957 Goebel et al. 2.997,493 A 8, 1961 Huber (71) Applicant: ETROLIAM NASIONAL BERHAD, 3,048,608 A 8, 1962 Girard et al. uala Lumpur (MY) 4,061,581. A 12/1977 Leleu et al. 4,298,730 A 11/1981 Gall tal. (72) Inventors: Daniel B. Garbark, Blacklick, OH 4,313,890 A 2, 1982 Ayyy a (US); Herman Paul Benecke, 5.362,368 A 1 1/1994 Lynn et al. Columbus, OH (US) 5,773.256 A 6/1998 Pellenc et al. 5,773,391 A 6/1998 Lawate et al. (73) Assignee: Petrolliam Nasional Berhad, Kuala 7,125,9506,107,500 AB2 10/20068, 2000 PE. 1 et al. al. Lumpur (MY) 7,192.457 B2 3/2007 Murphy et al. 7,589,222 B2 9/2009 Narayan et al. (*) Notice: Subject to any disclaimer, the term of this 2004/0167343 Al 8, 2004 Halpern et al. patent is extended or adjusted under 35 588. 5.5% A. $38. Sanarayan et al et al.1 U.S.C. 154(b) by 0 days. 2009/0216040 A1 8/2009 Benecke et al. 2009, 0239964 A1 9, 2009 Sasaki et al. (21) Appl. No.: 14/381,530 2010, 0087350 A1 4/2010 Sonnenschein et al. 2010/01 17022 A1 5, 2010 Carr et al. (22) PCT Filed: Feb. 28, 2013 2011/OO77350 A1 3/2011 Malotky et al. 2011/0269979 A1 11/2011 Benecke et al. (86). PCT No.: PCT/MY2013/000038 (Continued) T.S.O), Aug.e Aff27, 9 2014 FOREIGN PATENT DOCUMENTS AU 165032 2, 1954 (87) PCT Pub. No.: WO2013/129907 CN 101.077856 A 11/2007 PCT Pub. Date: Sep. 6, 2013 (Continued) (65) Prior Publication Data OTHER PUBLICATIONS US 2015/OO80599 A1 Mar. 19, 2015 Handbook of Chemistry and Physics (96th Edition, 2015-2016), pp. Related U.S. Application Data 6-210 to 6-228. European Search Report for EP13755664.3 dated Apr. 28, 2015. (60) Provisional application No. 61/604.267, filed on Feb. Akerman et al., “Biolubricant Synthesis. Using Immobilised Lipase: 28, 2012. Process Optimisation of Trimethylolpropane Oleate Production.” Process Biochem. 46:2225-2231 (2011). (51) Int. Cl. Translated Office Action for Chinese Application No. C07C 67/08 (2006.01) 201380022561.5, mailed Sep. 6, 2015. C07C 67/29 (2006.01) (Continued) C07C 67/39 (2006.01) CD7C 69/02 (2006.01) C07C 69/22 (2006.01) Primary Examiner — Paul A Zucker CD7C 69/34 (2006.01) Assistant Examiner — Mark Luderer 9. 975 R (74) Attorney, Agent, or Firm — LeClairRyan, a CIIC 3/04 3:08: Professional Corporation (52) U.S. Cl. CPC ............... C07C 67/29 (2013.01); C07C 67/08 (57) ABSTRACT CE. C. 02: CE. C. C Alkyl esters (butyl, hexyl, or other) of full composition palm (2013 01); C07C 69.675 (2013 01): CIIC fatty acids, palm fatty acid distillates (PFAD), and palm 3.oO6 (201 3.01): CIIC 3/04 (2013 01) kernel fatty acid distillates (PKFAD) can be used to generate 58) Field of Classification S h polyurethane and lubricant products. The alkyl esters of the (58) sC O as:fails yC 67/29: CO7C 67/39: present invention can be produced via Ozonolysis. The - - - - - - - CO7C 69/O2. CO7C 69/2 2. CO7C 69/3 4. improved method for producing alkyl esters includes react CO7C 69.675. C11C 3,006. C11C 3/04 ing at least one Substance having at least one carbon-to S lication file f s 1 h hi carbon double bond with ozone in the presence of least one ee application file for complete search history. monoalcohol that azeotropes with water. In particular, the (56) References Cited method may comprise reacting with at least one first mole of oZone and at least one second mole of oZone, and further U.S. PATENT DOCUMENTS comprises refluxing before addition of the second mole of OZO. 667.043 A 1/1901 Steep 2,401.338 A * 6, 1946 Dunmire ................. C11B 3.001 554,191 28 Claims, 5 Drawing Sheets US 9,505,701 B2 Page 2 (56) References Cited Spyros, A., “Quantitative Determination of the Distribution of Free Hydroxylic and Carboxylic Groups in Unsaturated Polyester and U.S. PATENT DOCUMENTS Alkyd Resins by 31 P-NMR Spectroscopy,” J. Appl. Polym. Sci., 83: 1635-1642 (2002). 2011/0269981 A1 11/2011 Benecke et al. PCT International Search Report and Written Opinion for Interna 2011/0269982 A1 11/2011 Benecke et al. tional Patent Application No. PCT/MY2013/000038 (Jun. 27. 2012fO184758 A1 7, 2012 Krull et al. 2013). 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Oil Palm Research, 15(2):42-49 (2003). * cited by examiner U.S. Patent Nov. 29, 2016 Sheet 1 of 5 US 9,505,701 B2 ---- | W are a areaware-wnwrigae are wrporaar U.S. Patent Nov. 29, 2016 Sheet 2 of 5 US 9,505,701 B2 Q U.S. Patent Nov. 29, 2016 Sheet 3 of 5 US 9,505,701 B2 U.S. Patent US 9,505,701 B2 ~~----------* U.S. Patent Nov. 29, 2016 Sheet S of 5 US 9,505,701 B2 9:"?IH US 9,505,701 B2 1. 2 METHOD FOR THE PRODUCTION OF eroxides to ester polyols. The main role of the solvent is to ESTERS AND USES THEREOF provide heat dissipation and cosolubilization of different types of reactants. Most organic solvents have little or no This application is a national stage application under 35 water. However, if water is present, water can react with U.S.C. 371 from PCT/MY2013/000038, filed Feb. 28, 2013, 5 certain intermediates to form unwanted products. which claims the benefit of U.S. Provisional Patent Appli A variation of the above approach involves the substitu cation Ser. No. 61/604,267, filed Feb. 28, 2012, each of tion of monoalcohols for primary polyols to form carboxylic which is hereby incorporated by reference in its entirety.